Apparatus for the Synthesis of Anhydrous Hydrogen Halide and Anhydrous Carbon Dioxide

ABSTRACT

An apparatus for the synthesis of anhydrous hydrogen halide fluids from organic halide fluids, such as perfluorocarbon fluids and refrigerant fluids, and anhydrous carbon dioxide for the environmentally safe disposition thereof.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional PatentApplication No. 61/474,657, filed on Apr. 12, 2011, which is herebyincorporated by reference as if fully set forth herein.

FIELD OF THE INVENTION

This invention relates to an apparatus for the synthesis of anhydroushydrogen halide and carbon dioxide. In thermo-catalytic reactor A,carbon dioxide is synthesized from carbon monoxide and water. Inthermo-catalytic reactor B, hydrogen halide fluids are synthesized fromorganic halide fluids, anhydrous hydrogen and anhydrous carbon dioxide.

BACKGROUND OF THE INVENTION

The organic halide family is very extensive. This invention is concernedwith the family of refrigerant fluids and perfluoro fluids. The chemicalsynthesis of a significant number of organic halide fluids have beenaccomplished during the last 80 years, including the majority ofrefrigerant fluids such as chlorofluorocarbons (hereinafter “CFCs”),hydrochlorofluorocarbons (“HCFCs”), fluorocarbons (“FCs”)hydrofluorocarbons (“HFCs”) and hydrofluoroalkenes (“HFOs”).

It has been established that some fluids, particularly compounds used asrefrigerants, have contributed to the depletion of ozone in theatmosphere and global warming. International action has been taken tophase out the use of these refrigerants and like compounds. Currently,the scientific community is concerned with protecting the environment,particularly with respect to any chemical contamination, including therelease of carbon dioxide to the atmosphere.

Currently, the treatment and/or decomposition of organic halide fluids,such as refrigerants, require an apparatus that can include the use ofextremely high temperatures. For example, certain apparatus for thedecomposition of refrigerants can require heating the compounds to atemperature of about 1,300° C. to 20,000° C. under reducing conditions.Thus, there exists a need for an apparatus for the treatment of organichalide fluids under less severe conditions; i.e. temperatures less than1,300° C.

SUMMARY OF THE INVENTION

Accordingly, the present invention is directed to a method for thesynthesis of anhydrous hydrogen halide and anhydrous carbon dioxide thatsubstantially obviates one or more of the problems due to limitationsand disadvantages of the related art.

Exemplary embodiments provide a new apparatus for the synthesis ofanhydrous hydrogen halide and carbon dioxide. In thermo-catalyticreactor A, carbon dioxide may be synthesized from carbon monoxide andwater. In thermo-catalytic reactor B, hydrogen halide fluids may besynthesized from organic halide fluids, hydrogen and anhydrous carbondioxide.

In an exemplary embodiment, dual reactors A and B of unit 1, wherein abattery of one or more dual reactors a thermo-catalytic reaction takesplace in reactor A of the first heat sink vessel, a thermo-catalyticreaction takes place in reactor B of the second heat sink vessel and thethird heat sink vessel provides the means for balancing the heat in thefirst and second heat sink vessels.

In one aspect, the embodiments provide an apparatus for thethermo-catalytic synthesis of anhydrous hydrogen halide fluids andanhydrous carbon dioxide. In thermo-catalytic reactor A, carbon dioxideand hydrogen are synthesized from carbon monoxide and water. Inthermo-catalytic reactor B, hydrogen halide fluids are synthesized fromorganic halide fluids, hydrogen and anhydrous carbon dioxide.

In another aspect, the embodiments provide an apparatus with dualreactors A and B, wherein reactor A, the reactants are carbon monoxideand water, which forms carbon dioxide and hydrogen with a low energyexothermic reaction in a pressure range from 1 atm to 30 atm and in atemperature range of 300° C. to 900° C. In reactor B the reactants areorganic halide fluids, anhydrous hydrogen and anhydrous carbon dioxide,which forms hydrogen halide fluids and carbon monoxide, in a pressurerange from 1 atm to 30 atm and in a temperature range of 600° C. to 900°C.

In another aspect, the embodiments provides an apparatus having ahydrogen diffuser where the hydrogen atom output is at least equal tothe number of halide atoms from the organic halide fluid.

In another aspect, the embodiments provide an apparatus having a masscontrol device to regulate the flow of carbon dioxide molecules to be atleast equal to the number of carbon atoms of the other reactants,forming the anhydrous hydrogen halide fluids and carbon monoxide.

In another aspect, the embodiments provide an apparatus for thethermal-catalytic decomposition of organic halide fluids such asrefrigerant fluids and perfluorocarbon fluids.

In another aspect, the embodiments provide an apparatus with athermo-catalytic reactor for the conversion of carbon monoxide and waterto hydrogen and carbon dioxide.

In another aspect, the embodiments provide an apparatus with athermo-catalytic reactor for the conversion of organic halide toanhydrous hydrogen halide and carbon monoxide.

In another aspect, the embodiments provide an apparatus with athermo-catalytic reaction (similar to a water-gas shift reaction)utilizing a catalyst for the conversion of carbon monoxide and water tohydrogen and carbon dioxide.

In another aspect, the embodiments provide an apparatus with athermo-catalytic reaction utilizing a catalyst for the conversion oforganic halide to anhydrous hydrogen halide and carbon monoxide.

In another aspect, the embodiments provide an apparatus to arrange thedual reactors A and B wherein energy input is not required to run thereaction.

In another aspect, the embodiments provide an apparatus to control thebalance between the halide atoms of the reactants and the hydrogen atomsto form only anhydrous hydrogen halide fluids.

In another aspect, the embodiments provide an apparatus to control thecarbon dioxide in reactor B that prevents any formation of carbon (soot)and to form only carbon monoxide.

In another aspect, the embodiments provide an apparatus with dualreactors. In reactor A there are no organic halides, organic chloridecompounds or molecular chlorine present and in reactor B there is nomolecular oxygen present, thus preventing the formation of dioxins andfurans.

In another aspect, the embodiments provide an apparatus for thesynthesis of hydrogen halide and carbon monoxide from the conversion ofhydrogen, carbon dioxide and organic halides, such as CFCs, HCFCs, FCsand HFCs, as the reactant fluids in the presence of a catalyst in thereaction zone of reactor B.

In another aspect, the embodiments provide an apparatus for anyhydrogen, carbon monoxide and/or carbon dioxide exiting from thehydrogen diffuser to be recycled to the inlet of reactor A.

Additional features and advantages of the invention will be set forth inthe description which follows, and in part will be apparent from thedescription, or may be learned by practice of the invention. Theobjectives and other advantages of the invention will be realized andattained by the structure particularly pointed out in the writtendescription and claims hereof as well as the appended drawings.

To achieve these and other advantages and in accordance with the purposeof the present invention, as embodied and broadly described, a systemfor treatment and/or decomposition of organic halide fluids comprising:a dual reactor unit having a first reactor within a first heat sinkvessel, a second reactor within a second heat sink vessel and a thirdheat sink balance vessel; wherein the first reactor and the secondreactor are fluidly connected such that a product of a reaction thatoccurs in one reactor is fed into the other reactor.

In another aspect of the present invention, a dual reactor unitcomprising: a first heat sink vessel including a first reactor, a secondheat sink vessel including a second reactor, a third heat sink balancevessel; and a circulator; wherein the first heat sink vessel is fluidlyconnected to the second heat sink vessel, the third heat sink balancevessel and the circulator.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory and areintended to provide further explanation of the invention as claimed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is one embodiment of the flow diagram arrangement of theapparatus 100 utilized by the present invention.

FIG. 2 is a diagram of one embodiment of a dual reactor unit 1 of theapparatus 100 utilized by the present invention.

DETAILED DESCRIPTION OF THE INVENTION

Although the following detailed description of the apparatus containsmany specific details for purposes of illustration, it is understoodthat one of ordinary skill in the art will appreciate that manyexamples, variations and alterations to the following details are withinthe scope and spirit of the invention. Accordingly, the exemplaryembodiments of the invention described herein are set forth without anyloss of generality to, and without imposing limitations thereon, theclaimed process invention.

Organic halide compounds and/or refrigerants fluids can include CFCs,HCFCs, FCs, HFCs and HFOs, that include at least of one fluid compound,such as refrigerant fluids including, but not limited to: R10(carbontetrachloride), R11 (trichlorofluoromethane), R12(dichlorodifluoromethane), R13 (chlorotrifluoromethane), R14(tetrafluoromethane), R21 (dichlorofluoromethane), R22(chlorodifluoromethane), R23 (trifluoromethane), R30 (methylenechloride), R31 (chlorofluoromethane), R32 (dichloromethane), R40(chloromethane), R41 (fluoromethane), R152a (difluoroethane), R110(chloroethane), R112 (chlorodifluoroethane), R113(trichlorotrifluoroethane), R114 (dichlorotetrafluoroethane), R115(chloropentafluoroethane), R116 (hexafluoroethane), R123(dichlorotrifluoroethane), R124 (chlorotetrafluoroethane), R125(pentafluoroethane), R134a (tetrafluoroethane), R1234YF(2,3,3,3-Tetrafluoropropene), R1234ZE (1,3,3,3-Tetrafluoropropene),R1243ZF (1,1,1-Tetrafluoropropene), R141b (dichlorofluoroethane), R142b(chlorodifluoroethane), R143a (trifluoroethane), and like compounds.Similarly, brominated refrigerants, such as R12B(bromochlorodifluoromethane) and R13B (bromotrifluoromethane), and otherrelated compounds having one or two carbon atoms and at least onebromine atom, can be treated according to the apparatus describedherein. As used herein a fluid is defined as any substance, (liquid, orgas) that has a low resistance to flow and that tends to assume theshape of its container. As used herein, organic halide refers tomolecules that include both carbon and a halogen, preferably includingbetween 1, 2, 3 and 4 carbon atoms, and at least one halogen atom permolecule. In certain embodiments, the organic halide and/or refrigerantinclude at least one carbon atom and at least one fluorine atom.

One aspect of the present apparatus invention is a dual reactor unitwherein two thermo-catalytic reactions may take place for the synthesisof anhydrous hydrogen halide and carbon dioxide. Both reactions may takeplace in a plasma free environment. In an exemplary embodiment, the dualreactor unit may include a reactor A and reactor B. Both reactors A andB may be thermo-catalytic reactor tubes. In reactor A, thethermo-catalytic reaction of carbon monoxide and water forms carbondioxide and hydrogen. In reactor B, the thermo-catalytic reaction of theorganic halide, hydrogen and carbon dioxide forms anhydrous hydrogenhalide products and carbon monoxide recycle fluid.

FIG. 1 is an exemplary embodiment of illustration of apparatus of system100. This exemplary embodiment includes a dual reactor unit 1, heatexchangers unit 2, hydrogen diffuser unit 3, a series of purifiedcollectors that may include anhydrous hydrogen fluoridepurifier/collector unit 4, hydrogen bromide purifier/collector unit 5,hydrogen chloride purifier/collector unit 6, a separatepurifier/collector unit such as a carbon dioxide purifier/collector unit7, dryer unit 8 and hydrogen halide neutralization scrubber unit 9. Thenine units are represented with a single digit. All accessories and/orcomponents of each unit are represented by two digits after the digitrepresenting the unit; i.e. the pipe connection of the gas inlet inscrubber unit 9 is represented by the number 902.

By following this numbering procedure, all the elements of the apparatus100 can be described as follows. Heat transfer fluid 190 in reactor unit1 is brought to the operating temperature via the external heating means126 of heat sink vessel 103. The heat transfer fluid 190 is circulatedby means of bi-directional flow circulator 104 from heat sink vessel 103via pipe connection 105 to heat sink vessel 101. From heat sink vessel101 heat transfer fluid 190 may flow via pipe connection 110 and 109 tobi-directional flow circulator 104 continuing via pipe connections 108and 107 to heat sink vessel 102. The heat transfer fluid 190 may flowfrom heat sink vessel 102, via pipe connection 106, back to heat sinkvessel 103. A means to heat balance heat sink vessel 103 is via inletpipe connection 120 and 121 and outlet pipe connections 122, 123 andflow control valve 124. Dual reactor unit 1 can be filled with ordrained of heat transfer fluid 190 via valve 137 and may be pressureprotected by safety relief valve 138.

In an exemplary embodiment, once an operating temperature is reached, aflow of carbon monoxide and water stream 990 enters reactor tube 112 inheat sink vessel 101 via pipe connection 125. The thermo-catalyticreaction of the carbon monoxide and water stream 990 takes place inreaction zone 111 assisted by catalyst 180. Any excess heat of reactionpasses through the diathermal wall of reactor tube 112 and may beabsorbed by heat transfer fluid 190. The reaction forms hydrogen,un-reacted carbon monoxide and carbon dioxide stream 191, which may exitreactor tube 112 via pipe connection 115.

The stream 191 enters the tube-in-tube heat exchanger 210 via pipeconnection 214 and may exit via pipe connection 215 and flows to thedryer unit 8 via pipe connection 802.

Dryer unit 8 may include vessel 801 with external heating means 806 forthe thermo-regeneration of the drying agent 895. Stream 191 exits dryer801 as anhydrous hydrogen, anhydrous un-reacted carbon monoxide andanhydrous carbon dioxide stream 191 via pipe connection 804, flowing togas compressor 805.

Exiting gas compressor 805, the stream 191 may enter the carbon dioxidepurifier/collector unit 7 via pipe connection 706. The carbon dioxidepurifier/collector unit 7 may include column 702, reflux condenser 703with cooling mean inlet 720 and outlet 721 and collector 701 withheating means inlet 722 and outlet 723, where the liquid carbon dioxide790 can be collected. The liquid carbon dioxide 790 in collector 701 canbe drained via pipe connection 708 and valve 726 to container connection707. After purification and collection of the carbon dioxide stream 790,stream 790 exits purifier/collector unit 701 via pipe connection 708.

In one exemplary embodiment, the carbon dioxide stream 790 may then beflowed to enter the tube-in-tube heat exchanger 210 via pipe connection212, flowing through inner tube 211. The wall of the inner tube 211 is adiathermal wall and transfers heat from the outside of the inner tube211 to the inside of the inner tube 211, therefore passing heat tostream 790 in the inner tube 211. Stream 790 exits via pipe connection213 and flows via pipe connections 120, 121, 122, 123, 119, 118 and 116and flow control valve 124 to reactor tube 114. In line valve 226 may beused only as a servicing valve.

In one embodiment, the hydrogen, un-reacted carbon monoxide and tracesof carbon dioxide stream 791 can exit from the top of purifier/collectorunit 7 via pipe connection 714 and flows to gas compressor 705. Thestream 791 exits gas compressor 705 and flows to hydrogen diffuser 301via pipe connection 303.

Hydrogen diffuser 301 may include an external heating means 310,hydrogen intake chamber 312 with palladium wall 302 and hydrogencollector 311. The hydrogen stream 390 may exit the hydrogen collectorof hydrogen diffuser 301 via pipe connection 304. The purified hydrogenstream 390 flow may be regulated by mass flow controller 308 operatingflow control valve 306 and 309. In one embodiment, the purified hydrogenstream 390 flows via pipe connections 119, 118 and 116 to reactor tube114. Any remaining hydrogen, carbon monoxide and carbon dioxide can exithydrogen diffuser 301 and may be recycled via pipe connection 319 and315, with valves 316 closed and 317 open, through gas compressor 305,check valve 318, pipe connection 135 and 128 in humidifier vessel 127with the wet gas flowing back to reactor tube 112 via pipe connection129 and 125. Optionally, when the hydrogen diffuser is in theregeneration mode, any remaining hydrogen, carbon monoxide and carbondioxide may exit hydrogen diffuser 301 via pipe connections 319 and 315,valve 316, with valve 317 closed, and diffuser exhaust 307 toatmosphere. The mass controller 308 also operates flow control valve 124to regulate the flow of carbon dioxide stream 790 and operates flowcontrol valve 209 to regulate the flow of organic halide 290.

In one embodiment, the flow of the organic halide fluid stream 290 maybe flowed through a tube-in-tube heat exchanger 201 from its connectedsource, to gas compressor 205 and pipe connection 203, passing throughheat exchanger 201 and exiting via pipe connection 206, flowing via flowcontrol valve 209 and pipe connections 118 and 116 to reactor tube 114.

The hydrogen stream 390, carbon dioxide stream 790 and organic halidefluid stream 290 come together, via pipe connection 116, and flow intoreactor tube 114. The thermo-catalytic reaction of the carbon dioxide,hydrogen and organic halide fluid may take place in reaction zone 113,may be assisted by catalyst 181, forming anhydrous hydrogen halide andanhydrous carbon monoxide stream 192. Stream 192 exits the reaction tube114 via pipe connection 117 and pipe connection 207, entering inner tube202 of tube-in-tube heat exchanger 201.

The wall of the inner tube 202 may be a diathermal wall and may transferheat from the inside of the inner tube 202 to the outside of the innertube 202, therefore passing heat to the organic halide fluid stream 290in the outer tube 201. The hydrogen halide and carbon monoxide stream192 exits tube-in-tube heat exchanger 201 via pipe connections 204 and280. The apparatus at this point may have at least two modes: (1) Themode of recovery of the hydrogen halide products (anhydrous hydrogenfluoride and/or anhydrous hydrogen bromide and/or anhydrous hydrogenchloride) may be by opening valve 281, closing valve 282, flowingthrough check valve 284 and entering the hydrogen fluoridepurifier/collector unit 4 via pipe connection 406. (2) The mode ofneutralizing the hydrogen halide products (anhydrous hydrogen fluorideand/or anhydrous hydrogen bromide and/or anhydrous hydrogen chloride)may be by opening valve 282, closing valve 281, flowing through checkvalve 283, to gas compressor 925 and entering scrubber vessel 901 viapipe connection 902, wherein the hydrogen halides are neutralized andthe carbon monoxide is recycled to heat sink vessel 101.

The anhydrous hydrogen fluoride purifier/collector unit 4 may includecolumn 402, reflux condenser 403 with cooling means inlet 420 and outlet421 and outlet 421, collector 401 where the liquid hydrogen fluoride 490can be collected and flow control valve 426. The liquid hydrogenfluoride 490 in collector 401 can be drained via pipe connection/diptube 408 and valve 426 to container connection 407. The hydrogenfluoride 490 present may be removed from the hydrogen halide and carbonmonoxide stream 192 at this point. In the event hydrogen fluoride 490 isthe only hydrogen halide present in the hydrogen halide and carbonmonoxide stream 192, the carbon monoxide stream 491 and any remaininghydrogen fluoride 490 may exit the hydrogen fluoride purifier/collectorunit 4 via pipe connection 414, flowing through valve 416 and 516,(bypassing hydrogen bromide purifier/collector unit 5 and hydrogenchloride purifier/collector unit 6 by closing valves 413, 513 and 616)to neutralizing scrubber unit 9 via check valve 920 and pipe connection902.

In the event hydrogen bromide and/or hydrogen chloride are present inhydrogen halide and carbon monoxide stream 192, the hydrogen halide andcarbon monoxide stream 192, along with any remaining hydrogen fluoride490, may exit hydrogen fluoride purifier/collector unit 4 via pipeconnection 414 and enters hydrogen fluoride removal trap 410 via pipeconnection 417, simultaneously closing valves 413 and 416 and openingvalve 415.

Any remaining hydrogen fluoride 490 is absorbed by the sodium fluoride411 in hydrogen fluoride removal trap 410. Hydrogen fluoride removaltrap 410 has an external heating means 418 which is used, when required,to desorb the trapped hydrogen fluoride 490 and flow the desorbedhydrogen fluoride 490 via pipe connection 412 (by simultaneously openingvalve 413 and closing valves 415, 416, 513 and 616) to neutralizingscrubber unit 9 via check valve 920 and pipe connection 902.

In the event there is hydrogen bromide and/or hydrogen chloride presentin hydrogen halide and carbon monoxide stream 192 they may be removedusing additional collectors. In such an embodiment, the hydrogenfluoride removal trap 410 may allow the hydrogen bromide and/or hydrogenchloride in hydrogen halide and carbon monoxide stream 192 to flowthrough valve 415 and gas compressor 505 to hydrogen bromidepurifier/collector unit 5 via pipe connection 506. The anhydroushydrogen bromide purifier/collector unit 5 consists of column 502,reflux condenser 503 with cooling means inlet 520 and outlet 521 andcollector 501 with heating means inlet 522, flow control valve 524 andoutlet 523, where the liquid hydrogen bromide 590 can be collected. Theliquid hydrogen bromide 590 in collector 501 can be drained via pipeconnection 508 and valve 526 to container connection 507. The hydrogenbromide 590 present will be removed from the hydrogen halide and carbonmonoxide stream 192 at this point. In the event hydrogen bromide 590 isthe only hydrogen halide still present in the hydrogen halide and carbonmonoxide stream 192, the hydrogen halide and carbon monoxide stream 192,with any remaining hydrogen bromide 590, exits the hydrogen bromidepurifier/collector unit 5 via pipe connection 514, flowing throughvalves 513 and 516, (bypassing hydrogen chloride purifier/collector unit6 by closing valves 515 and 616) to neutralizing scrubber unit 9 viacheck valve 920 and pipe connection 902.

If hydrogen chloride is present in the hydrogen halide and carbonmonoxide stream 192 exiting from hydrogen bromide purifier/collectorunit 5 via pipe connection 514, valve 513 may be closed with the flowthrough valve 515, gas compressor 605 and pipe connection 606. Theanhydrous hydrogen chloride purifier/collector unit 6 consists of column602, reflux condenser 603 with cooling means inlet 620 and outlet 621and collector 601 with heating means inlet 622, flow control valve 624and outlet 623, where the liquid hydrogen chloride 690 can be collected.The liquid hydrogen chloride 690 in collector 601 can be drained viapipe connection 608 and valve 626 to container connection 607. Thehydrogen chloride 690 will be removed from the hydrogen halide andcarbon monoxide stream 192 at this point. The remaining hydrogen halideand carbon monoxide stream 192 exits the hydrogen chloridepurifier/collector unit 6 via pipe connection 614, flowing through valve616, to neutralizing scrubber unit 9 via check valve 920 and pipeconnection 902.

Neutralizing scrubber unit 9 may include vessel 901, pipe connections902, 908, 909 and 914, caustic solution 903, H pattern valves 904, 905,906 and 907, pump 910 for circulation, filling, and draining causticsolution 903 in vessel 901, ph gauge 911, temperature gauge 912,pressure gauge 913, gas compressor 915, and valve 916. The carbonmonoxide stream 491 and any remaining hydrogen halide fluids entersneutralizing scrubber unit 9 via pipe connection 902 wherein thehydrogen halide fluids present are neutralized by caustic solution 903circulating in vessel 901 by pump 910. The ph level of caustic solution903 is monitored by ph gauge 911 and caustic solution 903 is replacedwhen required via the operation of H pattern valves 904, 905, 906, 907and pump 910. Carbon monoxide stream 491 exits neutralizing scrubberunit 9 via pipe connection 914 flowing to gas compressor 915 and (withvalve 916 closed) to humidifier vessel 127 via check valve 134 and pipeconnection 128.

Humidifier vessel 127 may contain water 130, may have a heating means131, and a temperature and water level control of standard design.Carbon monoxide stream 491 may flow through water 130 in humidifiervessel 127, adding water 130 to the gas flow. The carbon monoxide andwater stream 990 exits humidifier vessel 127 via pipe connection 129 andflows to reactor tube 112 via pipe connection 125. This completes theflow diagram of the apparatus 100.

The exemplary apparatus 100 may include multiple interconnected pieces,such as piping, valves, sensors and the like, can be constructed ofcarbon steel, stainless steel, Hastelloy, Monel, Inconel, Nickel, or alike material capable of operating at the temperatures and pressurescontemplated herein. Apparatus 100 may be suitable for thethermo-catalytic synthesis of anhydrous hydrogen halide fluids andcarbon monoxide from organic halide fluids, anhydrous hydrogen andanhydrous carbon dioxide and the thermo-catalytic synthesis of carbondioxide from carbon monoxide and water.

FIG. 2 is an illustration of an exemplary dual reactor unit 1 used inthis invention method. The dual reactor may include the followingcomponents: heat sink vessel 101, heat sink vessel 102, heat sink vessel103 for balancing the heat, thermo-catalytic reactor tube 112 withreaction zone 111 containing catalyst 180 and thermo-catalytic reactortube 114 with reaction zone 113 containing catalyst 181.

An exemplary operation of dual reactor unit 1 may be as follows: Theheat transfer fluid 190 in dual reactor unit 1 is brought to theoperating temperature via external heating means 126 of heat sink vessel103. The heat transfer fluid 190 is circulated by means ofbi-directional flow circulator 104 from heat sink vessel 103 via pipeconnection 105 to heat sink vessel 101. From heat sink vessel 101 theheat transfer fluid 190 flows via pipe connection 110 and 109 tobi-directional flow circulator 104 continuing via pipe connections 108and 107 to heat sink vessel 102. The heat transfer fluid 190 flows fromheat sink vessel 102 via pipe connection 106 back to heat sink vessel103. A means to balance the heat transfer fluid 190 is via inlet pipeconnection 120 and outlet pipe connection 122.

Once operating temperature is reached, the process in heat sink vessel101 may be as follows: A flow of carbon monoxide and water stream 990enters reactor tube 112 in heat sink vessel 101 via pipe connection 125.The thermo-catalytic reaction of the carbon monoxide and water stream990 takes place in reaction zone 111 assisted by catalyst 180. Anyexcess heat of reaction passes through the diathermal wall of reactortube 112 and is absorbed by heat transfer fluid 190. The reaction formsa hydrogen and carbon dioxide stream 191, which exits reactor tube 112via pipe connection 115.

The process in heat sink vessel 102 may be as follows: The hydrogenstream 791, carbon dioxide stream 790 and organic halide fluid stream290 come together at pipe connection 116 and flow into reactor tube 114.The thermo-catalytic reaction of the carbon dioxide, hydrogen andorganic halide fluid takes place in reaction zone 113 assisted bycatalyst 181. Any excess heat of reaction passes through the diathermalwall of reactor tube 114 and is absorbed by heat transfer fluid 190. Thereaction forms anhydrous hydrogen halide and carbon monoxide stream 192,which exits reactor tube 114 via pipe connection 117.

Any impermeable metallic wall that can transfer heat through themetallic wall is a diathermal wall and is part of the diathermal wall inreactor tubes 112 and 114 of dual reactor unit 1. Any impermeablemetallic wall that is in contact with the reactant is part of thereaction zones in reactor tubes 112 and 114 of dual reactor unit 1. Theheat produced by the exothermic reaction of water and carbon monoxide inheat sink vessel 101 causes the temperature of the reaction zone to beincreased to greater than the reaction temperature set point. Thereaction zone may be maintained at a reaction zone temperature ofbetween about 300° C. and 1000° C.

Anhydrous hydrogen fluoride collector unit 4, anhydrous hydrogen bromidecollector unit 5, anhydrous hydrogen chloride collector unit 6,anhydrous carbon dioxide collector unit 7, dryer 8 and neutralizingscrubber 9 are of standard engineering design. Other operationalrequirements may not require any of the above or may require some of theabove or may require additional components or may require anycombination of the above and/or additional components.

In general, the reaction of carbon monoxide and water in the apparatusmay be conducted at relatively low pressures. In certain embodiments,the reaction is carried out at pressures in the range of 1 atm to 30atm, preferably at pressures in the range of 10 atm to 20 atm. Incertain embodiments, the reaction is carried out at 15 atm.

In general, the reaction of the organic halide fluid, hydrogen andcarbon dioxide in the apparatus may be conducted at relatively lowpressures. In certain embodiments, the reaction is carried out atpressures in the range of 1 atm to 30 atm, preferably at pressures inthe range of 10 atm to 20 atm. In certain embodiments, the reaction iscarried out at 15 atm.

In certain embodiments, the flow of the anhydrous carbon dioxide andanhydrous hydrogen can be regulated by the apparatus depending upon theflow of the organic halide fluid being treated. For example, based uponthe heat of reaction, the amount of anhydrous carbon dioxide andanhydrous hydrogen can be adjusted by the apparatus to operate thereactor at a level to reduce any external supply of heating or cooling.

One exemplary embodiment provides an apparatus for utilizing dualreactors; with reactor tube 114 containing a catalyst consisting of atleast two metallic elements. The elements are selected from: atomicnumbers 4, 5, 13, and 14, transition metals with atomic numbers from 21to 29. 39 to 47, 57 to 71 and 72 to 79. In the presence of thesecatalysts the decomposition of the organic halide fluid is completed ata decreased temperature.

An alternative embodiment provides an apparatus for utilizing dualreactors; with reactor tube 112 containing a catalyst consisting of atleast two metallic elements. The elements are selected from: atomicnumbers 4, 5, 13, and 14, transition metals with atomic numbers from 21to 29, 39 to 47, 57 to 71 and 72 to 79. In the presence of thesecatalysts the synthesis of hydrogen and carbon dioxide from carbonmonoxide and water is obtained with the thermodynamic equilibrium beingreached at lower temperatures and pressures.

A catalyst may be used to assist in the prevention of the formation ofsome hazardous compounds such as dioxins and furans, to accelerate therate of reaction, to decrease the reaction temperature and/or to inducethe reactions. Transition metals may be used as catalysts in either orboth reactors. Exemplary metallic elements for the catalysts may beselected from the following:

ATOMIC NUMBER SYMBOL NAME  4 Be Beryllium  5 B Boron 13 Al Aluminum 14Si Silicon 21 Sc Scandium 22 Ti Titanium 23 V Vanadium 24 Cr Chromium 26Fe Iron 27 Co Cobalt 28 Ni Nickel 29 Cu Copper 39 Y Yttrium 40 ZrZirconium 41 Nb Niobium 42 Mo Molybdenum 44 Ru Ruthenium 45 Rh Rhodium46 Pd Palladium 47 Ag Silver 60 Nd Neodymium 66 Dy Dysprosium 74 WTungsten 77 Ir Iridium 78 Pt Platinum 79 Au Gold

In one embodiment the catalysts may be prepared by using a mixture ofmetallic elements in the form of alloys. Each reactor may use one ormore catalysts for the reaction. In the reactor for the synthesis ofcarbon dioxide and hydrogen the thermo-catalytic reaction of carbonmonoxide and water (the water-gas shift reaction) may be enhanced byusing a catalyst having two or more of the following elements: Al, Ni,Fe, Co, Pt, Ir, Cr, Mo, Cu, Pd, Rh, V and Au as the principal componentsof the alloy. In the reactor for the decomposition of organic halides,such as refrigerants and perfluorocarbon fluids, the thermo-catalyticreaction may be enhanced by using a catalyst having a blend of thefollowing elements: Nd, Nb, Dy, Fe, B, Pt, Pd, Rh, Y, Co, Ni, Cr, Mo,Al, Ir and W as the principal components of the alloy.

The physical form of each of the alloys used in the blend can beproduced in a variety of shapes, such as pellets, cylinders or flatsheets, with a preferable range of 0.5 mm to 5.0 mm in thickness, apreferable range of 10 mm2 to 100 mm2 in surface area per unit and aspecific surface area in cm2/g. The alloys are very compact metallicmaterials with less porosity than catalyst oxide supports, where thetypical specific surface area is measured in m2/g. In general thespecific surface area for alloy is measured in cm2/g.

The majority of catalyst supports are mineral oxides and all mineraloxides react with hydrogen halides. Therefore, mineral oxide catalystsupports are not used in this invention. As an alternative, thisinvention may use sintered metallic alloy catalyst supports. Sinteredmetallic alloy catalysts and catalyst supports are resistant tocorrosion by the hydrogen halide and high temperatures. Flat sheetparticles of metallic alloys with a thickness of 0.5 mm to 5.0 mm, aunit surface area from 10 mm² to 100 mm² and a range of the specificsurface area from 20 cm²/g to 80 cm²/g are used in the experimental unithowever, a unit for an industrial plant would likely use a specificsurface area in the range of 10 to 200 m²/g.

The catalysts prepared for the experimental work of this invention wereselected from alloys as follows:

-   -   Catalyst #1 consists of the elements Fe 50.0% wt, Ni 33.5% wt,        Al 14.0% wt, Co 0.5% wt, Ti 0.5% wt, Si 1.125% wt and Rh/Pt 0.5%        wt in an alloy form. True density of the alloy is in a range        from 2.0 g/cm3 to 10 g/cm3 and the bulk density of the catalysts        particles of the alloy is in a range from 0.25 to 0.5 g/cc.    -   Catalyst #2 consists of the elements Fe 63.0% wt, CR 18% wt, Mo        3% wt, Mn 2.0% wt, and Si 0.08% wt in an alloy form. True        density of the alloy is in a range from 2.0 to 10 g/cm³ and the        bulk density of the catalysts is in a range from 0.25 to 0.5        g/cc. Other catalysts equivalent to alloy #2 are Hastelloy C,        Inconel 600 and Stainless Steel 316    -   Catalyst #3 consists of the elements Fe 65.0% wt, Nd 29% wt, Dy        3.6% wt, Nb 0.5% wt, B 1.1% wt and Ir/Pt 0.08% wt in an alloy        form. True density of the alloy is in a range from 2.0 to 10        g/cm³ and the bulk density of the catalysts is in a range from        0.25 to 0.5 g/cc.    -   Catalyst #4 consists of the elements Pd 82.0% wt, Cu 17% wt and        Pt/Rh 1.0% wt in an alloy form. True density of the alloy is in        a range from 2.0 to 10 g/cm³ and the bulk density of the        catalysts are in a range from 0.25 to 0.5 g/cc.

The catalyst for the synthesis of anhydrous hydrogen halides, from thethermo-catalytic reaction of organic halides, hydrogen and carbondioxide, is a blend of about 50% of alloy #2 and 50% of alloy #3.

A laboratory bench scale unit was set up for conditioning the catalystsof this invention and the results obtained from the subsequent test runswere at a maximum pressure of 4 atm. The tests were (1) the reaction ofcarbon monoxide and water and (2) the reaction of organic halide withcarbon dioxide and hydrogen; with a comparison being made between theuse of no catalyst or improvements over other catalysts. Four stainlesssteel 316 reactor tubes were prepared, each having dimensions of 19 mmOD, 16 mm ID and 900 mm (90 cm) in length. Each tube has a crosssectional flow area of 200 mm², an internal wall surface of 45,000 mm²and an internal volume of about 180,000 mm³ (180 cm³).

In reactor tube #1, a stainless steel 316 sintered filter, having a 15mm OD and 75 mm length, was inserted in one end. A 75 g blend ofcatalyst #1 and catalyst #2 was then added to reactor tube #1, followedby another stainless steel 316 sintered filter, having a 15 mm OD and 75mm length, being inserted in the other end of reactor tube #1. Theprepared reactor tube #1 was set in a high temperature heating oven anda passivation procedure was initiated. The passivation process was toflow 20 ml/minute of hydrogen fluoride for three hours at 1,000° C. toform a layer of metal fluoride in the active surface area of thecatalyst. This was followed by a flow of 20 cc/minute of carbon dioxidefor one hour at 900° C. and for one hour with the heater turned off. Atthis point, the flow of carbon dioxide was stopped and the reactor tubewas opened to the atmosphere.

Reactor tube #2 is identical in construction and preparation to reactortube #1; however the catalyst was changed by substituting a 75 g blendof catalyst #2 and catalyst #3. The passivation procedure was identicalto reactor tube #1.

Reactor tube #3 is identical in construction to reactor tube #1, howeverit contained no filters or catalyst; i.e. an empty tube. There was nopassivation procedure used with reactor tube #3.

Reactor tube #4 is identical in construction and preparation to reactortube #1, however the catalyst was changed by substituting 75 g ofcatalyst #4. There was no passivation procedure used with reactor tube#4.

In another aspect, energy input may not be required for the apparatusarrangement of a battery of dual reactors.

EXAMPLES

The following reactions in the apparatus represent typical exothermicand endothermic reactions in which various illustrative organic halidefluids are thermo-catalytically formed into anhydrous hydrogen halideand carbon monoxide. The examples show the exothermic reactions having ahigher energy value than the endothermic reactions with the benefit thatthe excess of energy of the exothermic reaction balances the heatsensible of the reactant component. Following is the heat of formationand heat capacity table used for the examples:

Heat Capacity Heat of Formation Cal/mol ° C. @ constant Symbol Kcal/molΔHf 25° C. pressure @ 500° C. average CF₄ −220.5 14.56 CCl₂F₂ −114.217.54 CHClF₂ −113.0 13.28 C₂H₂F₄ 206.7 34.57 CO −26.4 7.21 CO₂ −94.010.77 H₂ 0.0 7.00 H₂O −58.0 8.54 HF −64.0 6.94 HCl −22.0 7.06

Example 1

Reactor tube #4 was heated to a temperature of 850° C. The CO flow meterwas set for a 22 cc/minute flow through a water humidifier, where the COjoined with 18 mg/minute of H₂O. The CO and H₂O were flowed into thereaction zone contacting the catalyst blend and the reaction of the COand H₂O formed CO₂ and H₂. During the nine minutes of collection, 390 ccof gaseous product with a cylinder pressure of 10 psig was collected ina sample cylinder having a 234 cc empty volume. The gaseous product wasanalyzed by a gas chromatograph with the only compounds detected beingCO at 50% by mol, CO₂ at 25% by mol and H₂ at 25% by mol.

CO+H₂O→C0₂+H2+ΔH_(R)

−26.00−58.00→−94.00+0.00

ΔHr=84.00ΔHp=−94.00

ΔH_(R25° C.)=ΔHp−ΔHr=−94.00+84.00=−10 Kcal/mol

CPr=+7.21=+8.54=+15.75 Cal/mol×degrees C.

CPp=+10.77+7.00=+17.77 Cal/mol×degrees C.

ΔCP=CPp−CPr=(17.75−15.75)=2×800=1600=1.6 Kcal/mol

ΔH_(R800° C.)=−10.00 Kcal/mol+1.60=−8.40 Kcal/mol

Exothermic Reaction

Example 2

Reactor tube #1 was heated to a temperature of 850° C. Three flow meterswere calibrated for (1) carbon tetrafluoride at 22 cc/minute, (2) carbondioxide at 22 cc/minute and (3) hydrogen at 44 cc/minute. The exhaustwas checked with an electronic organic halide detector and no carbontetrafluoride was detected. The product was collected for eight minutesinto a sample cylinder at a pressure of 29 psig with the product beingliquid anhydrous hydrogen fluoride. Partial pressure of anhydroushydrogen fluoride was 22 psia and partial pressure of the carbonmonoxide was 22 psia; the total pressure was 44 psia=29 psig.

GC-MS Analysis FTIR Analysis CF4 ND HF (anhydrous 2/1 Dioxins NDvapor/liquid)/CO Furans ND Hydrogen <1% Carbon dioxide <5%

CF₄+2H2+C02+→2CO+4HF+ΔHR

−220.50+0.00−94.00→−26.40−64.00

ΔH_(r)=−220.50−94.00=314.5

ΔH_(p)=−2(26.40)−4×64.00=−308.8

ΔH_(R25° C.)=−308.8+314.50=+5.700 Kcal/mol

CP_(r)=+14.56+2(7.00)+10.77=+39.33 Cal/mol×degrees C.

CP_(p)=+2(7.21)+4(6.94)=+42.18 Cal/mol×degrees C.

ΔCP=2.85×800=+2.28 Kcal/mol

ΔH_(R800° C.)=+5.70+2.28=+7.98 Kcal/mol

Endothermic Reaction

Example 3

Reactor tube #1 was heated to a temperature of 850° C. Three flow meterswere calibrated for (1) dichlorodifluoromethane at 22 cc/minute, (2)carbon dioxide at 22 cc/minute and (3) hydrogen at 44 cc/minute. Theexhaust was checked with an electronic organic halide detector and nodichlorodifluoromethane was detected. The product was collected foreight minutes into a sample cylinder at a pressure of 54 psi+/−1 psiwith the product being liquid anhydrous hydrogen fluoride and liquidanhydrous hydrogen chloride.

GC-MS Analysis Dichlorodifluoromethane (R-12) ND Dioxins ND Furans NDHydrogen <2% Carbon dioxide <6% Carbon monoxide 31% Hydrogen fluoride31% Hydrogen chloride 31%

CClF₂+₂H₂+C0₂+→₂CO+2HF+2HCl+ΔH_(R)

−114.20+0.00−94.00→−26.40−64.00−22.00

ΔH_(r)=−114.20−94.00=−208.20

ΔH_(p)=−2(112.40)=−224.8

ΔH_(R25° C.)=−224.8+208.20=−16.60 Kcal/mol

CP_(r)=+17.54+14.0+10.77=+42.31 Cal/mol×degrees C.

CP_(p)=+2(7.21+7.06+6.94)=+42.4 Cal/mol×degrees C.

ΔCP=(42.42−42.31)×800=+0.00 Kcal/mol

ΔH_(R800° C.)=−16.60 Kcal/mol

Exothermic Reaction

Example 4

Reactor tube #2 was heated to a temperature of 850° C. Three flow meterswere calibrated for (1) chlorodifluoromethane at 22 cc/minute, (2)carbon dioxide at 22 cc/minute and (3) hydrogen at 22 cc/minute. Theexhaust was checked with an electronic organic halide detector and nochlorodifluoromethane was detected. The product was collected for eightminutes into a sample cylinder at a pressure of 53 psi+/−1 psi with theproduct being liquid anhydrous hydrogen fluoride and liquid anhydroushydrogen chloride.

GC-MS Analysis Chlorodifluoromethane (R-22) ND Dioxins ND Furans NDHydrogen <1% Carbon dioxide <4% Carbon monoxide 38% Hydrogen fluoride40% Hydrogen chloride 20%

CHCl₂F₂+H₂+C0₂+→2CO+2HF+HCl+ΔH_(R)

−113.00+0.00−94.00→−26.40−64.00−22.00

ΔH_(r)=−113.00−94.00=−207.00

ΔH_(p)=−2(26.40)−2(64.00)−22=−202.8

ΔH_(R25° C.)=−202.8+207.20=+4.20 Kcal/mol

CP_(r)=+13.28+10.77+7.0=+31.05 Cal/mol×degrees C.

CP_(p)=+2(7.21)+2(6.94)+7.06=+35.36 Cal/mol×degrees C.

ΔCP=35.36−31.05=4.31×800=3.438.00 Cal/mol

ΔCP=3.438.00 Cal/mol/1000=3.44 Kcal/mol

ΔH_(R800° C.)=+4.20+3.45=+7.65 Kcal/mol

Endothermic Reaction

Example 5

Reactor tube #2 was heated to a temperature of 850° C. Three flow meterswere calibrated for (1) tetrafluoroethane at 22 cc/minute, (2) carbondioxide at 44 cc/minute and (3) hydrogen at 22 cc/minute. The exhaustwas checked with an electronic organic halide detector and notetrafluoroethane was detected. The product was collected for eightminutes into a sample cylinder at a pressure of 64 psi+/−2 psi with theproduct being liquid anhydrous hydrogen fluoride.

GC-MS Analysis Tetrafluoroethane (R-134a) ND Dioxins ND Furans NDHydrogen <2% Carbon dioxide <4% Carbon monoxide 48% Hydrogen fluoride48%

C₂H₂F₄+H₂+2C0₂+→4CO+4HF+ΔH_(R)

−206.70+0.00−94.00→−26.40−64.00

ΔH_(r)=−(206.70+188.00)=−394.70

ΔH_(p)=−4(90.40)−2(64.00)=−361.60

ΔH_(R25° C.)=−361.60+394.70=+33.00 Kcal/mol

CP_(r)=−(34.57+21.54+7.0)=−63.11 Cal/mol×degrees C.

CP_(p)=+4(7.21)+4(6.94)=+56.60 Cal/mol×degrees C.

ΔCP=−63.11−+56.60=−6.51×800=−5,208.00 Kcal/mol

ΔCP=−5,208.00/1000=−5.21 Kcal/mol

ΔH_(R800° C.)=+33.00−5.20=27.80 Kcal/mol

Endothermic Reaction

Example 6

Reactor tube #3, with no catalyst present, was heated to a temperatureof 850° C. Three flow meters were calibrated for (1) carbontetrafluoride at 22 cc/minute, (2) carbon dioxide at 22 cc/minute and(3) hydrogen at 44 cc/minute. The exhaust was checked with an electronicorganic halide detector and carbon tetrafluoride was detected. Thetemperature was increased to 950° C., the exhaust was checked with theelectronic organic halide detector and carbon tetrafluoride wasdetected. The temperature was increased to 1050° C., the exhaust waschecked with the electronic organic halide detector and carbontetrafluoride was detected. The temperature was increased to 1150° C.,the exhaust was checked with the electronic organic halide detector andno carbon tetrafluoride was detected. Example 6 proves that the catalystof this invention decreases the temperature required for the completedecomposition of the perfluorocarbon (carbon tetrafluoride) by about300° C.

Conclusions from the results of the examples are: (1) The excess ofhydrogen and carbon dioxide in the reaction of the decomposition oforganic halides, such as CFCs, HCFCs, FCs and HFCs does not affect thereaction and is beneficial in preventing the generation of soot, (2) theexcess of water in the reaction of carbon monoxide with water in thewater-gas shift reaction does not create any negative effect, (3) theexclusion of molecular oxygen in the process prevents the formation ofunwanted compounds, such as dioxins and furans, especially when chlorideor chlorine is present in the reaction zone and (4) the catalysts of theinvention decreases the temperature required for the completedecomposition of the organic halide by about 300° C.

Although the present apparatus invention has been described in detail,it should be understood that various changes, substitutions, andalterations can be made hereupon without departing from the principleand scope of the invention. Accordingly, the scope of the presentinvention should be determined by the following claims and theirappropriate legal equivalents.

The singular forms “a”, “an” and “the” include plural referents, unlessthe context clearly dictates otherwise.

Optional or optionally means that the subsequently described event orcircumstances may or may not occur. The description includes instanceswhere the event or circumstance occurs and instances where it does notoccur.

Ranges may be expressed herein as from about one particular value,and/or to about another particular value. When such a range isexpressed, it is to be understood that another embodiment is from theone particular value and/or to the other particular value, along withall combinations within said range.

Throughout this application, where patents or publications arereferenced, the disclosures of these references in their entireties areintended to be incorporated by reference into this application, in orderto more fully describe the state of the art to which the inventionpertains, except when these reference contradict the statements madeherein.

1. A system for treatment and/or decomposition of organic halide fluidscomprising: a dual reactor unit having a first reactor within a firstheat sink vessel, a second reactor within a second heat sink vessel anda third heat sink balance vessel; wherein the first reactor and thesecond reactor are fluidly connected such that a product of a reactionthat occurs in one reactor is fed into the other reactor.
 2. The systemof claim 1, wherein the first reactor is a thermo-catalytic reactor tubethat comprises a reaction zone and a catalyst, and wherein the secondreactor is a thermo-catalytic reactor tube that comprises a reactionzone and a catalyst.
 3. The system of claim 1, further comprising ascrubber and a humidifier fluidly connected to the first reactor suchthat fluid flows from the scrubber through the humidifier into the firstreactor and a first reaction product flows from the first reactor to afirst heat exchanger.
 4. The system of claim 1, further comprising adiffuser, a second heat exchanger, and a source of organic halide fluidconnected to the second reactor such that the organic halide fluid flowsthrough the second heat exchanger and then into the second reactor andfluid from the diffuser flows into the second reactor.
 5. The system ofclaim 1, wherein the dual reactor unit is connected to a first heatexchanger, the first heat exchanger is connected to a dryer, the dryeris connected to a first collector unit, and the first collector unit isconnected to a diffuser, wherein the diffuser is also independentlyconnected to the dual reactor unit.
 6. The system of claim 1, furthercomprising a first heat exchanger; a dryer; and a first collector unit;wherein the dual reactor unit, the first heat exchanger, the dryer, thefirst collector unit are fluidly connected such that a first reactionproduct flows from the first reactor into the first heat exchanger fromthe first heat exchanger into the dryer and from the dryer to the firstcollector unit.
 7. The system of claim 6, further comprising a diffuserconnected to the first collector unit and to the second reactor suchthat fluid flows from the first collector unit to the diffuser and fromthe diffuser to the second reactor.
 8. The system of claim 7, whereinthe first collector unit is also connected to the first heat exchangerand the first heat exchanger is further connected to the second reactorsuch that fluid flows from the first collector unit to the first heatexchanger and from the first heat exchanger to the second reactor. 9.The system of claim 7, further comprising a series of second collectorunits and a scrubber unit, wherein the second reactor is connected tothe series of second collector units and to the scrubber unit such thata second reaction product flows from the second reactor to the series ofsecond collector units and/or to the scrubber unit.
 10. The system ofclaim 9, wherein the series of second collector units comprises at leastone collector unit and wherein the series of second collector units isalso connected to the scrubber such that fluid flows from the series ofsecond collector units to the scrubber.
 11. The system of claim 9,further comprising a humidifier such that fluid flows from the diffuserto the humidifier and from the scrubber to the humidifier and from thehumidifier to the first reactor.
 12. The system of claim 9, furthercomprising a source of organic halocarbons connected to the secondreactor, and optionally a second heat exchanger such that the organichalocarbons flow into the second heat exchanger and from the second heatexchanger into the second reactor.
 13. The system of claim 1, furthercomprising a humidifier connected to the first reactor and to a diffusersuch that fluid flows from the first reactor to the diffuser, from thediffuser to the humidifier and from the humidifier to the first reactor.14. The system of claim 1, further comprising a dryer, a firstcollector, and a diffuser such that the dryer and the first collectorare in the flow path between the first reactor the diffuser.
 15. Thesystem of claim 1, further comprising a series of second collector unitsconfigured to receive a second reaction product from the second reactor;the series of second collector units further being configured totransfer a second reaction product to the first reactor.
 16. The systemof claim 1, further comprising a first heat exchanger unit; a secondheat exchanger unit; a hydrogen diffuser unit; a carbon dioxidecollector unit; one or more hydrogen halide collector units; a scrubberunit; a humidifier unit; an organic halide source; and a dryer unit;wherein the organic halide source and all the units are fluidlyconnected to the reactor units.
 17. The system of claim 16, wherein thedual reactor unit and the other units are arranged to produce hydrogenhalides as collectable products from the second reactor and carbondioxide as collectable product from the first reactor withoutenvironmental emissions.
 18. The system of claim 16, wherein any carbonmonoxide produced in the second reactor is recycled to the first reactorto be used as a reactant for the production of the carbon dioxide andhydrogen; and carbon dioxide and hydrogen produced in the first reactorare used as reactants with one or more organic halides in the secondreactor.
 19. A dual reactor unit comprising: a first heat sink vesselincluding a first reactor, a second heat sink vessel including a secondreactor, a third heat sink balance vessel; and a circulator; wherein thefirst heat sink vessel is fluidly connected to the second heat sinkvessel, the third heat sink balance vessel and the circulator.
 20. Thedual reactor unit of claim 19, further comprising an external heatingsource connected to the third heat sink balance vessel; a first pipeconnecting the first heat sink vessel to the third heat sink balancevessel; a second pipe connecting the second heat sink vessel to thethird heat sink balance vessel; a fourth pipe connecting the first heatsink vessel to the circulator; and a fifth pipe connecting the secondheat sink vessel to the circulator.